Synthesis and properties of boron doped ZnO nanorods on silicon substrate by low-temperature hydrothermal reaction

Boron doped ZnO nanorods were fabricated by hydrothermal technique on silicon substrate covered with a ZnO seed layer. It is found that the concentration of boric acid in the reaction solution plays a key role in varying the morphology and properties of the products. The growth rate along the [0 0 0 1] orientation (average size in diameter) of the doped ZnO nanorods decreased (increased) with the increase of boric acid concentration. Based on the results of XRD, EDX and XPS, it is demonstrated that the boron dopants tend to occupy the octahedral interstice sites. The photoluminescence of the ZnO nanorods related to boron doping are investigated.     

掺银氧化锌纳米棒的水热法制备研究

利用水热法在直流磁控溅射制备的掺铝氧化锌 (AZO) 种子层上制备了不同形貌和光学性能的掺银ZnO纳米棒, 并采用XRD、扫描电镜、透射谱、光发射谱和EDS谱详细研究了Ag离子与Zn离子的摩尔百分比 (R_Ag/Zn) 及AZO种子层对掺银ZnO纳米棒的结构和光学性质的影响. 随着R_Ag/Zn的增加, 掺银ZnO 纳米棒的微结构和光学性质的变化与银掺杂诱导的纳米棒的端面尺寸变化有关. 平均端面尺寸的变化归结于种子层颗粒大小和颗粒数密度不同导致掺入的Ag离子的相对比例不同. 溅射15 min的AZO种子层上生长的ZnO纳米棒由于缺陷增多导致在可见光区的发光峰明显强于溅射10 min 的AZO种子层上、相同R_Ag/Zn 条件下生长的ZnO纳米棒. Ag掺杂产生的点缺陷增多导致可见光区PL波包较宽. 纯ZnO纳米棒的微结构与种子层厚度导致的结晶度和颗粒大小有关. 关键词： ZnO纳米棒 水热法 Ag掺杂 直流磁控溅射     

Ag-doped ZnO nanorods synthesized by two-step method

A two-step method is adopted to synthesize Ag-doped ZnO nanorods.A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate.Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method.The influences of the molar percentage of Ag ions to Zn ions(RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry,scanning electron microscopy and spectrophotometry.Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions.The<002>c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases.At RAg/Zn >1.0%,ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice.The average transmissivity in the visible region first increases and then decreases as R Ag/Zn increases.The absorption edge is first blue shifted and then red shifted.The influence of Ag doping on the average head face,and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn <1.0%.     

Drop‐cast and dye‐sensitized ZnO nanorod‐based visible‐light photodetectors

We report the facile fabrication of metal–semiconductor–metal (MSM) photodetectors with dye‐sensitized ZnO nanorods (NRs) operating at wavelengths of ～405–638 nm by a simple drop casting method. The ZnO NRs were synthesized by the hydrothermal synthesis method at 75 °C. The droplet of ethanol solution containing ZnO NRs was dropped between two metal electrodes and dried at 65 °C, which allows the ZnO NRs to be adhered and contacted to both metal electrodes. When a violet light of 405 nm was illuminated into the MSM ZnO NRs‐based photodetector, the photocurrent gain was obtained as ～3.9 × 10³ at the applied bias voltage of 5 V. By increasing the bias voltage from 10 V to 15 V, the device exhibited good recovery performance with a largely reduced reset time from 85.68 s to 2.47 s and an increased on–off ratio from 17.9 to 77.4. To extend the photodetection range towards the long visible spectral region, the ZnO NRs were sensitized by the N719 dye and then drop‐cast. The dye‐sensitized ZnO NRs‐based photodetector also exhibited good photocurrent switching under 638 nm of light illumination. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

醋酸锌热解温度对ZnO纳米棒的结构及光学性质的影响

采用水热法在普通载玻片上热解醋酸锌生成的ZnO种子层上制备ZnO纳米棒, 采用 X射线衍射仪、扫描电镜、分光光度计等测试手段详细研究了醋酸锌热解温度对 ZnO纳米棒的结构和光学性质的影响. 结果表明: 纳米棒的结晶质量、端面尺寸、宏观应力和透射率与醋酸锌热解温度有密切关系. 随着热解温度的增加, ZnO纳米棒具有的c轴择优取向性先增强后减弱, 拉应力先减小后增大, 可见光区的平均透射率先增大后减小. 热解温度为350 ℃时, ZnO纳米棒c轴择优取向性最强, 拉应力最小, 平均透射率最大. 端面尺寸诱导的表面散射 是影响ZnO纳米棒可见光区平均透射率的主要机制. 关键词： 醋酸锌 水热法 ZnO纳米棒     

Effects of Mn‐doping on surface acoustic wave properties of ZnO films

Surface acoustic wave (SAW) filters based on Mn‐doped ZnO films have been fabricated and effects of Mn‐doping on SAW properties are investigated. It is found that the electromechanical coupling coefficient (K²) of Zn_0.913Mn_0.087O films is 0.73 ± 0.02%, which is 73.8% larger than that of undoped ZnO films (0.42 ± 0.02%). Zn_0.913Mn_0.087O film filters also exhibit a lower absolute value of insertion loss (|IL|) of 16.1 dB and larger bandwidth (BW) of 5.9 MHz compared with that of undoped ZnO film filter. However, Zn_0.952Mn_0.048O film filters exhibit a smaller K² of 0.34 ± 0.02%, larger |IL| of 26.9 dB and smaller BW of 3.5 MHz. It is suggested that the SAW properties can be improved by appropriate Mn‐doping and Mn–ZnO/Si multilayer structure with large d₃₃ is promising for wide‐band and low‐loss SAW applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Au/TiO2 nanorod‐based Schottky‐type UV photodetectors

TiO₂ nanorods (NRs) were synthesized on fluorine‐doped tin oxide (FTO) pre‐coated glass substrates using hydrothermal growth technique. Scanning electron microscopy studies have revealed the formation of vertically‐aligned TiO₂ NRs with length of ～2 µm and diameter of 110–128 nm, homogenously distributed over the substrate surface. 130 nm thick Au contacts using thermal evaporation were deposited on the n‐type TiO₂ NRs at room temperature for the fabrication of NR‐based Schottky‐type UV photodetectors. The fabricated Schottky devices functioned as highly sensitive UV photodetectors with a peak responsivity of 134.8 A/W (λ = 350 nm) measured under 3 V reverse bias. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

过渡金属掺杂ZnO的电子结构和光学性质

利用基于密度泛涵理论的超软赝势法(USPP)，结合局域密度近似(LDA)，对过渡族金属离子掺杂的纤锌矿型ZnO做第一性原理计算，得到了它的平衡晶格常数、结合能、电子态密度分布、能带结构、介电函数、光学吸收系数等性质，详细讨论了掺杂后ZnO化合物的电子结构及成键情况，并结合实验结果定性分析了掺杂后光学性质的变化. 关键词： 氧化锌 掺杂 第一性原理 光学性质     

Fe和Ni共掺杂ZnO的电子结构和光学性质

基于密度泛函理论的第一性原理研究Fe,Ni单掺杂和(Fe,Ni)共掺杂纤锌矿型ZnO的能带结构、电子态密度分布、介电函数、光学吸收系数,分析了掺杂后电子结构与光学性质的变化.计算结果表明：掺杂体系的费米能级附近电子态密度主要来源于Fe 3d,Ni 3d态电子的贡献;与纯净ZnO相比,Fe,Ni单掺杂和(Fe,Ni)共掺杂ZnO的介电函数虚部均在0.46eV左右出现了一个新峰;Fe,Ni单掺杂和共掺杂ZnO的吸收光谱均发生明显的红移,并都在1.3eV处出现较强吸收峰.结合他人的计算和实验结果,给出了定性的讨 关键词： 氧化锌 掺杂 第一性原理 光学性质     

Synthesis and optical properties of ZnO nanorods on indium tin oxide substrate

ZnO nanorods with uniform diameter and length have been synthesized on an indium-tin oxide (ITO) substrate by using a simple thermal evaporation method which is suitable to larger scale production and without any catalyst or additives. The samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-vis (UV-vis) absorption spectrum, photoluminescence (PL) spectrum and Raman spectrum. The single-phase ZnO nanorods grow well-oriented along the c-axis of its wurtzite structure on ITO substrate. The ZnO nanorods shows sharp and strong UV emission located at 380 nm without notable visible light emission in the PL spectrum, which suggests the good crystallinity of the nanorods, which was also testified by their Raman spectrum. The photodegradation of methylene orange (MO) in aqueous solution reveals that the well-arranged c-axis growth of ZnO nanorods possess evidently improved photocatalytic performance and these properties enable the ZnO nanorods potential application in UV laser.     

Resistive switching characteristics of sol–gel based ZnO nanorods fabricated on flexible substrates

The authors report the resistive switching characteristics of sol–gel based ZnO nanorods (NRs) fabricated on flexible substrates. A resistance ratio of 10, endurance of over 100 cycles, and narrower dispersion in the ON/OFF voltages and resistances compared to ZnO thin‐film devices are demonstrated. Furthermore, the resistive switching characteristics on flexible substrates are maintained under severe substrate bending because of the ductile properties of the nanorods. Devices composed of the Au/sol–gel based NRs/Au structure have the potential for low‐temperature flexible nonvolatile memory applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructure and optical properties of nitrogen-doped ZnO film

The nitrogen doping of ZnO film deposited by the magnetron sputtering method is subsequently realized by the hydrothermal synthesis method.The nitrogen-doped ZnO film is preferably(002) oriented.With the increase of hexamethylenetetramine(HMT) solution concentration,the average grain size of the film along the 002 direction almost immediately decreases and then monotonously increases,conversely,the lattice strain first increases and then decreases.The structural evolution of the film surface from compact and even to sparse and rough is attributed to the enhanced nitrogen doping content in the hydrothermal process.The transmission and photoluminescence properties of the film are closely related to grain size,lattice strain,and nitrogen-related defect arising from the enhanced nitrogen doping content with HMT concentration increasing.     

Al，Ga掺杂ZnO电子结构和光电特性的第一性原理计算

采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,计算了本征ZnO,Al掺杂ZnO(ZnAlO)和Ga掺杂ZnO(ZnGaO)的能带结构、态密度、复介电函数和复电导率. 其中Al或Ga是以替位杂质的形式进入ZnO晶格. 计算结果表明纤锌矿型ZnO,ZnAlO和ZnGaO都是直接带隙半导体材料,掺杂后ZnO的带隙变小,且ZnAlO的带隙略大于ZnGaO. 掺杂后ZnO的电子结构发生变化,费米能级由本征态时位于价带顶上移进入导带,ZnO表现为n型掺杂半导体材料,掺杂后在导带底出现大量由掺杂原子贡献的自由载流子—电子,明显提高了电导率和介电函数,改善了ZnO的导电性能,并且ZnAlO的导电性能要略好于ZnGaO.     

Al，Ga掺杂ZnO电子结构和光电特性的第一性原理计算

采用基于密度泛函理论(DFT)框架下广义梯度近似(GGA)的PBE平面波超软赝势方法,计算了本征ZnO,Al掺杂ZnO(ZnAlO)和Ga掺杂ZnO(ZnGaO)的能带结构、态密度、复介电函数和复电导率. 其中Al或Ga是以替位杂质的形式进入ZnO晶格. 计算结果表明纤锌矿型ZnO,ZnAlO和ZnGaO都是直接带隙半导体材料,掺杂后ZnO的带隙变小,且ZnAlO的带隙略大于ZnGaO. 掺杂后ZnO的电子结构发生变化,费米能级由本征态时位于价带顶上移进入导带,ZnO表现为n型掺杂半导体材料,掺杂后在导带底出现大量由掺杂原子贡献的自由载流子—电子,明显提高了电导率和介电函数,改善了ZnO的导电性能,并且ZnAlO的导电性能要略好于ZnGaO.     

Cu-Fe共掺杂ZnO电子结构与光学性质的第一性原理计算研究

基于密度泛函理论的第一性原理平面波超软赝势方法,计算了本征ZnO,Cu、Fe单掺杂和Cu-Fe共掺杂ZnO的电子结构和光学性质.计算结果显示:Cu掺杂属于p型掺杂,Fe掺杂属于n型掺杂,单掺杂时Cu-3d态电子和Fe-3d态电子均在禁带形成杂质能级,从而提高ZnO的载流子浓度,改善ZnO的导电性能,而Cu-Fe共掺杂时ZnO半导体进入简并态,呈现金属特性.掺杂后的ZnO介电函数虚部变化主要集中在低能量区域,光谱吸收系数及反射率曲线发生红移,其中本征ZnO对太阳光谱有较好的透射性,Fe单掺杂和Cu-Fe共掺杂ZnO对可见光谱有相似的吸收效果,而Fe单掺杂ZnO对近紫外区域的光谱透射率更小,适用于制备防紫外线薄膜.     

A study of transition from n-to p-type based on hexagonal WO3 nanorods sensor

Hexagonal WO3 nanorods are fabricated by a facile hydrothermal process at 180 ℃ using sodium tungstate and sodium chloride as starting materials. The morphology, structure, and composition of the prepared nanorods are studied by scanning electron microscopy, X-ray diffraction spectroscopy, and energy dispersive spectroscopy. It is found that the agglomeration of the nanorods is strongly dependent on the PH value of the reaction solution. Uniform and isolated WO3 nanorods with diameters ranging from 100 nm-150 nm and lengths up to several micrometers are obtained at PH = 2.5 and the nanorods are identified as being hexagonal in phase structure. The sensing characteristics of the WO3 nanorod sensor are obtained by measuring the dynamic response to NO2 with concentrations in the range 0.5 ppm-5 ppm and at working temperatures in the range 25 ℃-250 ℃. The obtained WO3 nanorods sensors are found to exhibit opposite sensing behaviors, depending on the working temperature. When being exposed to oxidizing NO2 gas, the WO3 nanorod sensor behaves as an n-type semiconductor as expected when the working temperature is higher than 50 ℃, whereas, it behaves as a p-type semiconductor below 50 ℃. The origin of the n- to p-type transition is correlated with the formation of an inversion layer at the surface of the WO3 nanorod at room temperature. This finding is useful for making new room temperature NO2 sensors based on hexagonal WO3 nanorods.     

ZnO and ZnS Nanostructures: Ultraviolet-Light Emitters,Lasers, and Sensors

ZnO and ZnS, well-known direct bandgap II–VI semiconductors, are promising materials for photonic, optical, and electronic devices. Nanostructured materials have lent a leading edge to the next generation technology due to their distinguished performance and efficiency for device fabrication. As two of the most suitable materials with size- and dimensionality-dependent functional properties, wide bandgap semiconducting ZnO and ZnS nanostructures have attracted particular attention in recent years. For example, both materials have been assembled into nanometer-scale visible-light-blind ultraviolet (UV) light sensors with high sensitivity and selectivity, in addition to other applications such as field emitters and lasers. Their high-performance characteristics are particularly due to the high surface-to-volume ratios (SVR) and rationally designed surfaces. This article provides a comprehensive review of the state-of-the-art research activities in ZnO and ZnS nanostructures, including their syntheses and potential applications, with an emphasis on one-dimensional (1D) ZnO and ZnS nanostructure-based UV light emissions, lasers, and sensors. We begin with a survey of nanostructures, fundamental properties of ZnO and ZnS, and UV radiation–based applications. This is followed by detailed discussions on the recent progress of their synthesis, UV light emissions, lasers, and sensors. Additionally, developments of ZnS/ZnO composite nanostructures, including core/shell and heterostructures, are discussed and their novel optical properties are reviewed. Finally, we conclude this review with the perspectives and outlook on the future developments in this area. This review explores the possible influences of research breakthroughs of ZnO and ZnS nanostructures on the current and future applications for UV light–based lasers and sensors.     

Preparation of ZnO nanorods on cellulose fiber paper and their charge‐generating application for waste paper recycling

Zinc oxide (ZnO) nanorod arrays (NRAs) were well integrated on the cellulose fibers (CFs) of waste paper via a facile hydrothermal method. By mechanically blending the waste paper with de‐ionized water, abundant CFs were obtained and used as a sufficient platform for integrating ZnO NRAs. After coating a thin ZnO seed layer onto the surface of CFs and subsequent thermal treatment, the ZnO NRAs were densely grown, exhibiting high crystallinity and good photoluminescence properties. Their sizes were readily controlled by changing the concentration of the growth solution. To test the feasibility of an energy harvesting application using the prepared samples, the piezoelectric charge generation was explored under an external pushing force for the fabricated devices with polydimethylsiloxane‐shielded ZnO NRAs on CFs for good contact to two electrodes (i.e., gold and indium tin oxide). This nanotechnology of recycling waste paper could be considered as a promising candidate for implementation in cost‐effective and environment‐friendly advanced materials and energy production. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)